TW201500425A - Resin composition for high dielectric constant materials, molded article containing same, and master batch for coloring - Google Patents

Abstract

This resin composition for high dielectric constant materials contains 40-80% by mass of (A) a resin material and 20-60% by mass of (B) a carbon black. The carbon black (B) has a DBP absorption of 10-50 mL/100 g and an iodine adsorption of 5-40 mg/g. This resin composition for high dielectric constant materials has a dielectric constant of 4 or more and a dielectric loss tangent of 0.05 or less.

Description

Resin composition for high dielectric constant materials, molded articles including the same, and masterbatch for coloring

The present invention relates to a resin composition for a high dielectric constant material which is suitable for a material having a high dielectric constant, a molded article thereof, and a masterbatch for coloring.

<Prior Art 1>

In the past, a material for surface mounting antennas in which an electrode is disposed on a surface of a mobile communication device or the like, which is used in a mobile phone or the like, has been proposed as a material composed of a ceramic-containing resin composition. For example, there is a resin composition in which a spherical dielectric ceramic powder (for example, Patent Document 1) is mixed in a ratio of 40 vol% to 70 vol% (% by volume) based on the composition of the resin material.

However, the resin composition composed of the ceramic powder and the resin must increase the amount of the ceramic powder to obtain a high dielectric constant, and as a result, the specific gravity becomes high, and there is a problem that the antenna cannot be reduced in weight. Further, when the resin composition is molded, the obtained molded article is brittle in texture and has a problem in terms of impact resistance. When applied to a communication machine represented by a mobile phone, It is often necessary to withstand the impact resistance of falling down.

In order to make the resin material conductive, it is generally a carbon material-based particle such as graphite or carbon black. In particular, in the case of carbon black, when the blending amount is lower than the percolation threshold, high dielectric constant can be achieved while maintaining the insulating property, and the literature reviews the frequency dependence of the dielectric constant and its temperature dependence. (for example, Non-Patent Document 1).

However, since carbon black is extremely difficult to knead, when the amount of addition is increased in order to achieve high dielectric constant, the dispersion of carbon black is poor, which causes a problem that the resin composition is hard to be melted, or flow marks are formed in the appearance of the molded article. Further, when such a resin composition is used as a material for an antenna, it is necessary to transmit and receive a radio wave signal by using a metal, and therefore it is required that the molded article has good plating characteristics. However, in order to achieve a high dielectric constant, in the case where the amount of addition of carbon black is increased, the dispersion failure causes the carbon black to float on the surface of the molded article, and there is a problem that the peel strength of the plating film is insufficient.

On the other hand, several means for improving the impact resistance of the molded article of the resin composition are also known. One of the methods is to blend an olefin-based copolymer into a resin (see, for example, Patent Document 2). However, among resin compositions having a high dielectric constant, a general substrate resin is a polyphenylene sulfide (PPS) resin or a liquid crystal polymer, and a sufficient impact resistance improvement effect cannot be obtained. Further, if the base resin is intended to use a polycarbonate resin excellent in impact resistance, a representative high dielectric ceramic titanium oxide or an alkaline earth metal salt of a titanate may have a catalyst for hydrolyzing the polycarbonate resin. Function, it can not be used. This is because the problem that the resin viscosity is largely lowered occurs in a processing step in which high heat is applied, such as extrusion molding.

In addition, it is known that a base resin and a resin having high impact resistance are combined to form a two-color molded article (see, for example, Patent Document 3). However, the two-color molded article in which PPS or a liquid crystal polymer is compounded with a polycarbonate resin having high impact resistance has a weak interfacial adhesion and cannot obtain sufficient impact resistance. As such, attempts to impart sufficient impact resistance to molded articles of a resin composition having a high dielectric constant have not been successful.

<Prior Art 2>

In the past, when the thermoplastic resin was colored black, it was widely used to mix powder or granular carbon black in a powder, granule or mixture of powder and powder of the resin or resin composition, and melt-kneaded and extruded by an extruder. And it is broken and made into a granular form. However, in this method, when the carbon black powder is directly blended into the resin or the resin composition, there is a problem that the fine powder causes work environment pollution, workability, and even classification or agglomeration causes carbon black particles to occur, in the subsequent There are problems with residual colors, color mixing, etc. in the production lot.

Therefore, there is a method in which carbon black is dispersed in a resin at a high concentration to produce a master batch, and the masterbatch is used to color the resin. This coloring method does not cause carbon black scattering, and is excellent in handleability, and is now becoming the mainstream of resin coloring methods.

However, in the method as described above, the dispersion of the carbon black particles is not sufficient, and it is difficult to blend in a large amount. In the resin composition colored by the master batch, the carbon black particle aggregate "particles" are observed on the surface of the molded article produced, and the appearance is not good (see, for example, Patent Document 4).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 3930814

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-177015

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-026646

[Patent Document 4] Japanese Laid-Open Patent Publication No. 61-236854

[Non-patent literature]

[Non-Patent Document 1] Nakamura, "Interpretation of Dielectric Properties of Carbon Black and Polyethylene Composites Below the Percolation Threshold", Electrical Society Paper A, Electrical Society, Heisei 11, Vol. 119, No. 11, p .1355~1361

An object of the present invention is to provide a resin composition for a high dielectric constant material which is excellent in dielectric constant, dielectric loss tangent, appearance, and the like, and a molded article including the same. Further, another object of the present invention is to provide a masterbatch for coloring which is easily mass-produced, and which is less likely to cause appearance defects in a colored resin molded article.

As a result of review by the present inventors, it has been found that a resin composition having a high dielectric constant and a low dielectric loss tangent can be obtained by blending a specific carbon black in a resin material in a specific amount.

One aspect of the present invention is a resin composition containing (A) a resin material and (B) carbon black, characterized in that: (B) the characteristics of carbon black are specific DBP (dibutyl phthalate) absorption and specific iodine adsorption capacity. Thereby, it is possible to easily obtain a resin composition suitable for use in a high dielectric constant material, particularly an antenna member.

The present invention is as follows, for example.

[1] A resin composition for a high dielectric constant material, which comprises a resin composition for a high dielectric constant material containing (A) a resin material of 40 to 80% by mass and (B) a carbon black of 20 to 60% by mass. And the DBP absorption amount of the (B) carbon black is 10 to 50 (mL/100 g) and the iodine adsorption amount is 5 to 40 (mg/g), and the dielectric ratio of the resin composition for the high dielectric material is used. When it is 4 or more, the dielectric loss tangent is 0.05 or less.

[2] The resin composition for a high dielectric constant material according to [1], wherein the (A) resin material is 50 to 60% by mass and the (B) carbon black is 40 to 50% by mass, and the above (B) The DBP absorption of carbon black is 25~35 (mL/100g) and the iodine adsorption amount is 10~30 (mg/g).

[3] The resin composition for a high dielectric constant material according to [1] or [2], wherein the (B) carbon black has a nitrogen adsorption specific surface area of 5 to 40 m ² /g.

[4] The resin composition for a high dielectric constant material according to any one of [1] to [3], wherein the (B) carbon black has a ratio of a nitrogen adsorption specific surface area to an iodine adsorption amount of less than 1.3. .

[5] The resin composition for a high dielectric constant material according to any one of [1] to [4] wherein the (A) resin material is a polycarbonate resin, a denatured polyphenylene ether resin, or a polyphenylene. Thioether resin or polycarbonate/ABS alloy.

[6] The resin composition for a high dielectric constant material according to [5], wherein the (A) resin material is a polycarbonate resin.

[6] The resin composition for a high dielectric constant material according to any one of [1] to [6] wherein the surface pH of the (B) carbon black is 3 to 8.

[7] A molded article comprising the resin composition for a high dielectric constant material according to any one of [1] to [6-1].

Further, as a result of review by the present inventors, it has been found that by blending a specific amount of specific carbon black into a polycarbonate resin, a high dielectric having a high dielectric constant, a low dielectric loss tangent, and thermal stability can be obtained. The resin composition for a material and a molded article obtained by molding a two-color resin with a polycarbonate resin solve the above problems and complete the present invention.

The present invention is as follows, for example.

[8] A molded article comprising carbon black (b) containing a polycarbonate resin (a) and a DBP absorption amount of 10 to 50 (mL/100 g) and an iodine adsorption amount of 5 to 40 (mg/g). A resin composition (C) and a polycarbonate resin for a high dielectric material having a carbon black (b) content of 20 to 60% by mass, and a carbon black (b) content of 40 to 80% by mass. (D) obtained by two-color molding.

[8] The molded article according to the above [8], wherein the content of the polycarbonate resin (a) in the resin composition (C) for a high dielectric constant material is 50 to 60% by mass, the aforementioned The content of the carbon black (b) is 40 to 50% by mass, the DBP absorption amount of the carbon black (b) is 25 to 35 (mL/100 g), and the iodine adsorption amount is 10 to 30 (mg/g).

[8-2] The molded article according to [8] or [8-1], wherein the aforementioned high The resin composition (C) for a dielectric material has a dielectric constant of 4 or more and a dielectric loss tangent of 0.05 or less.

[8-3] A molded article obtained by two-color molding of a resin composition (C) and a polycarbonate resin (D) for a high dielectric constant material according to the above [6].

[8] The molded article according to any one of [8] to [8-3] wherein the carbon black (b) has a nitrogen adsorption specific surface area of 5 to 40 m ² /g.

[8] The molded article according to any one of [8] to [8-4] wherein the ratio of the nitrogen adsorption specific surface area to the iodine adsorption amount of the carbon black (b) is less than 1.3.

[8] The molded article according to any one of [8], wherein the polycarbonate resin (a) has a viscosity average molecular weight of 15,000 to 25,000.

[9] The molded article according to any one of [8], wherein the molded article is a resin composition (C) layer for the high dielectric constant material and the polycarbonate resin. The layer (D) is composed of a polycarbonate resin (D) layer having a thickness of 0.1 mm to 5 mm.

[10] The molded article according to any one of [8], wherein the resin composition (C) for the high dielectric constant material and/or the polycarbonate resin (D) contains an inorganic filler. material.

As a result of further examination by the inventors of the present invention, it has been found that a masterbatch for coloring which can solve the above problems can be obtained by using a carbon black having a specific DBP (dibutyl phthalate) absorption amount, and the present invention has been completed.

The invention is as follows.

[11] A masterbatch for coloring comprising a masterbatch for coloring of (E) carbon black and (F) a resin material, and the DBP absorption amount of the (E) carbon black is 10 to 50 (mL/100 g), The (E) carbon black has an iodine adsorption amount of 10 to 30 (mg/g).

[12] The masterbatch for coloring according to [11], wherein the DBP absorption amount is 25 to 35 (mL/100 g).

[13] The masterbatch for coloring according to [11] or [12], wherein the content of the (E) carbon black is 10 to 90% by mass, and the content of the (F) resin material is 10 to 90% by mass. %.

[14] The masterbatch for coloring according to [13], wherein the content of the (E) carbon black is 40 to 90% by mass, and the content of the (F) resin material is 10 to 60% by mass.

[15] The masterbatch for coloring according to any one of [11], wherein the (F) resin material is selected from the group consisting of a polycarbonate resin, a polystyrene resin, and a polyamide resin. One or more of the group consisting of a polyester resin and a polyacetal resin.

[16] The masterbatch for coloring according to [15], wherein the resin material is a polycarbonate resin.

[16] The masterbatch for coloring according to any one of [11] to [16] wherein the surface pH of the (E) carbon black is from 3 to 8.

[17] The masterbatch for coloring according to any one of [11] to [16-1], which further contains a thermal stabilizer.

[18] A molding material comprising the coloring master batch described in any one of [11] to [17], and a colored resin.

According to the present invention, it is possible to provide a resin composition for a high dielectric constant material having excellent dielectric constant, dielectric loss tangent, appearance, and the like, and a molded article comprising the same. Further, a masterbatch for coloring can be provided, which is easy to mass-produce, and the colored resin molded article is less likely to cause poor appearance.

<1st aspect>

The fat composition for a high dielectric constant material according to the first aspect of the present invention contains (A) a resin material and (B) carbon black having specific physical properties. (B) Carbon black is characterized by a low DBP absorption amount and a small amount of iodine adsorption.

(A) Resin material

The resin material of the resin composition substrate for a high dielectric constant material is preferably a dielectric loss tangent lower. The resin may be either a thermoplastic resin or a thermosetting resin, and a thermoplastic resin which can be injection molded is preferred. For example, low density polyethylene, ultra low density polyethylene, ultra ultra low density polyethylene, high density polyethylene, low molecular weight polyethylene, ultra high molecular weight polyethylene, ethylene-propylene copolymer, polypropylene, acrylonitrile/butyl a polyolefin-based resin such as a diene/styrene copolymer (ABS resin), an alloy of a polyphenylene ether resin and a polystyrene resin, an alloy of a polyphenylene ether resin and a polyamide resin, and a polyphenylene ether resin. A denatured polyphenylene ether resin such as an alloy of a polyolefin resin or a polycarbonate resin. Polybutylene terephthalate a polyester resin represented by a diester resin or a polyethylene terephthalate resin, a polyamide resin represented by a polydecylamine 6, a polyamide amine 66, a polyamide amine MXD6, or the like, or a polyacetal resin. Engineering plastics or alloys containing these. Further, it is also possible to use a super-engineered plastic having high heat resistance such as a liquid crystal polymer, a polyphenylene sulfide resin or a polyimide resin, or an alloy containing the same.

Among them, a polycarbonate resin, a denatured polyphenylene ether resin, a polyphenylene sulfide resin, or a polycarbonate/ABS alloy is preferable, and polycarbonate resin and polyphenylene are used from the viewpoint of excellent moldability and heat resistance. Denatured polyphenylene ether obtained by alloying an ether resin and a polystyrene resin is particularly preferable.

(B) carbon black

The carbon black used in the present invention has a DBP absorption of 10 to 50 (mL/100 g) and an iodine adsorption amount of 5 to 40 (mg/g). Ideally, the DBP absorption is 25 to 35 (mL/100 g), and the iodine adsorption amount is 10 to 30 (mg/g). The method for measuring the amount of DBP absorption is described in JIS K6217-4:2001, and is expressed by the volume (mL/100 g) of DBP absorbed per 100 g. Further, a method for measuring the amount of iodine adsorption is described in JIS K6217-1:2008, and is expressed by the amount of iodine (mg/g) adsorbed per unit weight of carbon black. They are all customary carbon black characteristics.

In general, carbon black exists in a state in which particles are welded to each other and is called an aggregate. Conceptually, a grape bunch is exemplified. The degree of development of this aggregate is called organization, and the indicator indicating the degree of development of the organization is the amount of DBP absorption. The iodine adsorption amount is the most representative index for determining the total specific surface area including the pores of the carbon black particles.

The smaller the amount of iodine adsorption, the smaller the specific surface area of the carbon black particles, and the lower the possibility that the particles in the resin composition are in contact with each other. When the DBP absorption amount is small, the degree of development of the tissue is low, and the connection resulting from the fusion of the particles is not developed. That is, carbon black having these characteristics, even if added in a large amount to the resin, is easily insulated by the resin between the particles. Further, since the percolation threshold is high, insulation can be maintained, and it is considered that the dielectric properties can be imparted to the resin composition, and the dielectric properties are high dielectric constant and low dielectric loss tangent.

In the case where the DBP absorption amount of carbon black is higher than 50 (mL/100 g) or the iodine adsorption amount is higher than 40 (mg/g), the carbon black particles in the resin composition are in contact with each other, and the frequency of electrical connection increases. The dielectric loss tangent increases. This also means that the carbon black particles are easily dispersed poorly in the resin composition, so that the dispersion is poor during melt kneading, and the separated carbon black tends to adhere to the vicinity of the mold. As a result, it is difficult to produce pellets in a stable manner, and an appearance defect such as a flow mark may occur in the injection molded article, and it is difficult to obtain a molded article having an excellent appearance.

Although the developed carbon black is easy to obtain a resin composition having a high dielectric constant, there is a problem that the directionality of the aggregate causes an anisotropy of the dielectric property, or the percolation causes a problem that the dielectric loss tangent increases. In particular, it is not suitable for use as an antenna member.

When the carbon black having a DBP absorption of less than 10 (mL/100 g) is produced, the adhesion of the apparatus for adhering to the carbon black particles is increased in the production of carbon black, and it is difficult to continuously operate (JP-A-2011-98995). Therefore, it is difficult to stably obtain such carbon black. In addition, carbon black having an iodine adsorption amount of less than 5 (mg/g) is not sold at home and abroad, and it is difficult to purchase it stably.

The (B) carbon black used in the present invention is only required to have a specific DBP absorption amount. There is no limitation on the type of iodine adsorption, and it can be appropriately selected depending on the purpose. For example, the oil furnace black produced by incomplete combustion of the feedstock oil by the oil furnace method, the acetylene black produced by the special furnace method, and the acetylene black produced by using acetylene gas as a raw material can be used in a sealed space. The lamp black produced by direct combustion of the raw material, the hot carbon black produced by thermal decomposition of natural gas, and the groove black accumulated by the diffusion flame contacting the bottom surface of the channel steel. Commercially available products are known as "Asahi #8" or "Asahi thermal" (Asahi Carbon Co., Ltd.).

Further, the surface pH of the carbon black may be slightly alkaline or neutral to acidic, and in the case where the (A) resin material is polycarbonate or polyester, these resins tend to be hydrolyzed by a base. Therefore, (B) carbon black should be neutral to acidic, and the surface pH should be 3-8.

In one embodiment, the nitrogen adsorption specific surface area (N ₂ SA) of the (B) carbon black is preferably 5 to 40 m ² /g, more preferably 10 to 30 m ² /g. Similarly to the iodine adsorption amount, the nitrogen adsorption specific surface area is a total specific surface area of the carbon black, and is a useful carbon black characteristic index. The nitrogen adsorption specific surface area can be measured in accordance with JIS K6217-2. The nitrogen adsorption specific surface area of carbon black is in the above range, and is similar to the iodine adsorption amount in terms of dielectric constant, dielectric loss tangent, and the like.

Further, the ratio of the nitrogen adsorption specific surface area to the iodine adsorption amount (N ₂ SA/IA) is preferably less than 1.3, and preferably less than 1.1. By adding carbon black having a N ₂ SA/IA in the above range by the amount of addition described later, a resin composition having a relatively excellent dielectric constant and dielectric loss tangent can be obtained. This resin composition can exhibit stable dielectric properties.

In the resin composition for a high dielectric constant material, the content of the (A) resin material and the (B) carbon black are (A) 40 to 80% by mass and (B) 20 to 60% by mass, respectively. It is desirable to contain (A) a resin material in an amount of 50 to 60% by mass and (B) a carbon black in an amount of 40 to 50% by mass. As long as it is carbon black having the specific DBP absorption amount and iodine adsorption amount, the carbon black particles do not percolate in this range, and a resin composition having a high dielectric constant and a low dielectric loss tangent can be obtained. In addition, characteristics such as dielectric characteristics or percolation thresholds are theoretically dependent on the volume fraction. When the (B) carbon black content is 20 to 60% by mass, it is approximately 15 to 55% by volume based on the volume fraction.

In order to improve the thermal stability of the resin composition during the production and molding steps, or the thermal stability in the high-temperature gas atmosphere when the product is used, it is preferred to incorporate a thermal stabilizer into the resin composition for the high dielectric material. The thermal stabilizer is preferably a hindered phenol compound, a phosphite compound, a phosphinate compound, or zinc oxide.

Further, other components may be added as necessary in the resin composition for a high dielectric constant material. Examples of such an additive include a filler, a reinforcing material, a weather resistance improver, a foaming agent, a lubricant, a fluidity improver, a wash resistance improver, a dye, a pigment, a dispersant, and the like.

For example, the filler or the reinforcing agent may be any of organic or inorganic, and usually uses glass fiber, mica (mica, biotite, phlogopite, etc.), alumina, talc, ettringite, potassium titanate, carbonic acid. An inorganic substance such as calcium or cerium oxide is preferred. These materials are preferably blended in an amount of from 1 to 100 parts by mass, preferably from 5 to 80 parts by mass, more preferably from 5 to 60 parts by mass, per 100 parts by mass of the total of the (A) resin material and the specific (B) carbon black. If this kind of thing is blended Quality, in general, can improve rigidity, heat resistance, dimensional precision and the like. Among these, in particular, muscovite or alumina is preferred because it has an effect of lowering the dielectric loss tangent. The blending amount of the muscovite or the alumina is preferably 5 to 100 parts by mass, and preferably 10 to 50 parts by mass, based on 100 parts by mass of the total of the (A) resin material and the specific (B) carbon black.

For example, the anti-crushing agent is not particularly limited as long as it is generally blended with a resin composition and can improve the punching resistance, and specifically, SBS (styrene-butadiene-styrene), Styrene-butadiene block polymer such as SEBS (styrene-ethylene-butylene-styrene) and its hydride, SIS (styrene-isoprene-styrene), SEPS (styrene-ethylene) a styrene-isoprene block polymer such as propylene-styrene, a hydride, an olefin elastomer, a polyester elastomer, a polyoxyn rubber, an acrylate rubber, or a methyl group a multilayer structure polymer of an alkyl acrylate polymer, a composite rubber-based graft copolymer obtained by graft-polymerizing a composite rubber composed of a polyoxymethylene rubber and an acrylate rubber component with a vinyl monomer. Wait. The amount of the substance to be blended is preferably 3 to 20 parts by mass, and preferably 5 to 10 parts by mass, based on 100 parts by mass of the total of the (A) resin material and the specific (B) carbon black.

The resin composition for a high dielectric constant material of the present invention contains (A) a resin material and a specific (B) carbon black, and can be produced, for example, by a step of melt-kneading (A) a resin material and a specific (B) carbon black. Further, it can also be obtained by a method of removing a solvent from a varnish which is formed by uniformly dispersing a solvent for dissolving a resin material.

The DBP absorption of (B) carbon black used in this application is 10~ 50 (mL/100 g), and the iodine adsorption amount is 5 to 40 (mg/g), and the dispersibility in the molten resin is good as compared with the ordinary carbon black exceeding the upper limit of the numerical range. Therefore, the resin composition for a high dielectric constant material of the present invention is suitably produced by melt-kneading by an extruder.

The melt-kneading can be performed by, for example, blending (B) carbon black in the (A) resin material, and if necessary, blending the heat stabilizer or additive as described above, by a Henschel mixer, a ribbon blender After uniformly mixing the V-type blender, the uniaxial or multi-axis mixing extruder, the roll mill, the Banbury mixer, the Labo Plastomill mixer (Brabender mixer), etc. are heated, and the mixture is kneaded in a molten state. Come on. In addition, several components may be mixed in advance or may be supplied during the kneading process without premixing, instead of mixing and kneading all the components together.

The kneading temperature and the kneading time will vary according to the type of the resin composition or the kneading machine used for the high dielectric constant material, and the usual kneading temperature is 200 to 350 ° C, preferably 220 to 320 ° C, and the kneading time system. It is better to use less than 20 minutes. When it exceeds 350 ° C or 20 minutes, thermal deterioration of the resin material may become a problem, and there may be a case where the physical properties of the molded article are lowered or the appearance is poor. The resin composition pellet for a high dielectric constant material obtained in this manner may be a molding method generally used for a thermoplastic resin, for example, an injection molding method, an extrusion molding method, a hollow molding method, a thermoforming method, a calender molding method, or the like. It is made into a molded article. From the viewpoint of productivity and product performance, an injection molding method is preferred.

The resin composition for a high dielectric material of the present invention can be easily produced. In addition, there is no flow mark or the like in the appearance of the injection molded article, and it is good because This is suitable for antenna parts. In order to reduce the size of the antenna component, the dielectric composition of the resin composition is preferably 4 or more, preferably 6 or more, more preferably 8 or more, and particularly preferably 9 or more. This is because if the dielectric constant is small, the antenna component cannot be made small enough. From the viewpoint of miniaturization, the upper limit of the dielectric constant is not particularly limited. However, if the dielectric constant is too large, the antenna size is too small. Therefore, it is preferably 30 or less in practical use, preferably 14 or less, and 12 or less. Better, 11 or less is especially good. The smaller the dielectric loss tangent is, the higher the efficiency of the radio wave emitted by the antenna is, and the longer the battery is, the better the temperature is 0.05 or less, preferably 0.03 or less, and particularly preferably 0.01 or less.

In the case where the molded article using the resin composition is an antenna component, the antenna pattern is formed on the surface of the molded article. However, in the case of using the resin composition for the high dielectric material, the standard ABS can be used. The pattern is easily formed by electroless copper plating or the like. The electroless copper plating treatment generally includes a pretreatment, a chemical etching, a catalyst addition, an activation, and an electroless plating step. In the chemical etching step, the formation of fine concavo-convex shapes by surface roughening greatly affects the plating metal and The adhesion of the resin. Since the carbon black of the specific DBP absorption amount is excellent in dispersibility in the resin, it does not overflow even if the amount of the carbon black is high, and even if the surface is roughened, the carbon black particles are not easily released on the surface of the molded article. Therefore, the adhesion between the resin composition and electroless copper plating is good.

[Example A]

The above first aspect will be further described in detail by way of examples, but the invention is not limited thereto. Further in the following embodiments, Each component uses the items disclosed below.

(A) Resin material

(a1) polycarbonate resin

Mitsubishi Engineering Plastics Co., Ltd., "Product Name: S-3000FN"

(a2) polyphenylene ether resin

Poly 2,6-dimethyl-1,4-phenylene ether (hereinafter abbreviated as "PPE"); Mitsubishi Engineering Plastics Co., Ltd. product, "trade name; PX100L", 30 ° C ultimate viscosity measured in chloroform 0.47dl/g.

(a3) Impact-resistant polystyrene resin (hereinafter abbreviated as "HIPS")

"Polymer name: HT478", manufactured by Japan Polystyrene Co., Ltd., weight average molecular weight of 200,000, MFR of 3.0 g/10 minutes (however, measured under conditions of 200 ° C × 5 kg).

(B) carbon black

(b1) Asahi Carbon Co., Ltd., "Product Name: Asahi #8"

(b2) Asahi Carbon Co., Ltd., "Product name: Asahi thermal"

(b3) Asahi Carbon Co., Ltd., "Product Name: Asahi #15"

(b4) Asahi Carbon Co., Ltd., "Product Name: Asahi #35"

(b5) Donghai Carbon Co., Ltd., "Product Name: Seast TA"

(b6) Donghai Carbon Co., Ltd., "Product Name: Seast S"

(b7) Donghai Carbon Co., Ltd., "Product Name: TOKA BLACK #7270SB"

(b8) manufactured by Tokai Carbon Co., Ltd., "Product Name: TOKA BLACK #7100F"

The physical properties of the carbon black used were summarized in Table A below.

(C) Thermal stabilizer

(c1) 肆(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite; manufactured by Ciba Specialty Chemicals, Inc., "Product Name: IRGAFAS P-EPQ"

(c2) ginseng (2,4-di-t-butylphenyl) phosphite; manufactured by Adeka Argus Co., Ltd., "trade name: ADK STAB 2112"

Examples A1 to A10 and Comparative Examples A1 to A7

The polycarbonate resin, the polyphenylene ether resin, the polystyrene resin, the carbon black, and the heat stabilizer were blended at a ratio shown in Table 1 and Table 2, and uniformly mixed by a roller mixer. This was put into an upstream part of a twin-screw extruder ("Steel 30 α", screw diameter 30 mm, L/D=63) manufactured by Nippon Steel Co., Ltd., and melt-kneaded at a cylinder temperature of 265 ° C and a screw rotation speed of 400 rpm. A pellet of the resin composition is produced. After the obtained pellets were dried at 100 ° C for 4 hours, the evaluations of the following (1) and (2) were carried out. The evaluation results are disclosed in Tables 1 and 2.

(evaluation method) (1) Dielectric properties

The resin composition pellet obtained by the above method was produced by using an injection molding machine (IS100F, manufactured by Toshiba Machine Co., Ltd., clamping force 100t) at a cylinder temperature of 290 ° C to 310 ° C and a mold temperature of 100 ° C. A plate-shaped molded article of 100 mm × 100 mm × 3 mm in thickness was used, and a dielectric constant and a dielectric loss tangent were measured at 1 GHz at room temperature using a material analyzer (manufactured by Agilent, 4291 A).

Further, the dielectric properties of the polycarbonate free of carbon black alone and the modified polyphenylene ether were used as reference examples A1 and A2, and are disclosed in Table 2.

(2) Appearance

The resin composition pellet obtained by the above method was produced under the conditions of a cylinder temperature of 290 ° C to 310 ° C and a mold temperature of 100 ° C using an injection molding machine (IS100F, manufactured by Toshiba Machine Co., Ltd., clamping force 100 t). A plate-shaped molded article of 100 mm × 100 mm × 3 mm in thickness. The flow marks generated on the obtained molded article were visually evaluated for appearance. The visual evaluation was performed by a score of 5 points (5 points: very good, 4 points: good, 3 points: slightly good, 2 points; slightly bad, 1 point: bad).

(3) Plating characteristics

Using the plate-shaped molded article used for the evaluation of the appearance of Example A4 and Comparative Example A4, the steps of pretreatment, chemical etching, catalyst addition, activation, and electroless plating were performed by standard ABS using electroless copper plating conditions to form a thickness. A 2 μm copper film was used to produce a plating coating. The adhesion of the coating was evaluated by JIS-H8504-15 (peeling test). On the plating film of the plating-coated body, the entire object to be plated was scored in the longitudinal and lateral directions at intervals of 2 mm, and scores were scored to form 25 lattice-shaped checkerboards. Then, a cellophane tape CT-18 made of Nichiban Co., Ltd., which satisfies the provisions of JIS Z1522, is attached to the lattice checkerboard and peeled off forcefully. The residual rate of the film after peeling off the tape was evaluated by counting the number of the aforementioned checkerboards remaining on the surface of the coating.

In the plate-shaped molded article used in Example A4, peeling of the plating film was not observed, and the residual ratio of the film was 100%. On the other hand, the film remaining ratio of the molded article used in Comparative Example A4 was 0%. Further, in the molded article used in Comparative Example A4, carbon black adhered to the plating film after peeling. The resin composition of Comparative Example A4 contained (110 mL/100 g) #7100F having a large DBP absorption amount, and therefore it was observed that carbon black was scattered on the surface of the molded article.

It is understood from the table that the resin molded article for high dielectric constant of Examples A1 to A10 has excellent dielectric properties and is easy to manufacture, and the molded article is excellent in appearance. On the other hand, it is also known that the molded articles containing Comparative Examples A2 to A7 which are not carbon black specified in the present invention have poor dielectric properties, and in particular, dielectric loss tangent increases. In addition, the appearance of the molded article is poor. Further, it is also known that even if the carbon black specified in the present invention is used, if the content is small, the improvement in dielectric constant is insufficient.

The resin composition associated with the first aspect described above has excellent dielectric properties, and is particularly suitable as a high dielectric material used in an antenna member which requires a high dielectric constant and a low dielectric loss tangent. In addition, it has excellent mechanical strength and can be easily mass-produced, and the appearance or plating adhesion of the molded article is also good. Since the specific gravity of carbon black is smaller than that of ceramic powder, it is possible to achieve miniaturization and weight reduction of the antenna. Therefore, the resin composition associated with the first aspect described above is suitable for materials for antenna parts such as mobile phones.

<Second aspect>

The molded article associated with the second aspect of the present invention is a two-color molded article of a resin composition (C) for a high dielectric constant material and a polycarbonate resin (D), and a resin composition for the high dielectric material. The system contains a polycarbonate resin (a) and a carbon black (b) characterized by a low DBP absorption amount and a small iodine adsorption amount.

(1) Polycarbonate resin

The molded article of the present invention has a resin as a high dielectric material. The polycarbonate resin (a) of the base resin of the composition (C); and the polycarbonate resin (D) which is a composite target material in the two-color molding. Any of them is not particularly limited and a well-known polycarbonate resin can be used. A well-known polycarbonate resin may, for example, be a thermoplastic aromatic polycarbonate resin, an aliphatic polycarbonate resin or an aromatic-aliphatic polycarbonate resin, and among them, an aromatic polycarbonate resin is preferred. The aromatic polycarbonate resin is generally obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid.

The aromatic dihydroxy compound may, for example, be 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene. Hydroquinone, resorcinol, 4,4-dihydroxybiphenyl, etc., preferably bisphenol A. Further, in order to further improve the flame retardancy, a compound obtained by combining one or more of the above-mentioned aromatic dihydroxy compounds with a tetraalkylphosphonium sulfonate or a polymer having a decyloxy group structure and having a phenolic OH group at both ends may be used. Oligomer.

The aromatic polycarbonate resin to be used in the invention may, for example, be a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane or 2,2-bis(4-hydroxyphenyl). a polycarbonate copolymer derived from propane and other aromatic dihydroxy compounds. Further, two or more kinds of polycarbonate resins may be used in combination.

The resin composition (C) for a high dielectric constant material needs to contain a large amount of carbon black of 20 to 60% by mass, and also needs to have sheet formability. Therefore, the polycarbonate resin (a) as the base resin is preferably a polycarbonate resin having a lower viscosity. Specifically, the solvent is methylene chloride, and the temperature is 25 ° C. The viscosity average molecular weight converted from the measured solution viscosity is preferably 15,000 to 25,000. The resin composition (C) for a high dielectric constant material and the polycarbonate resin (D) of the composite target material can be used without particular limitation as long as it has a molecular weight which exhibits the original impact resistance of the polycarbonate resin. The viscosity average molecular weight is preferably 20,000 to 30,000. From the viewpoint of mechanical strength and formability, it is preferred to use a polycarbonate having a viscosity average molecular weight within the above range.

(2) carbon black (b)

The carbon black used in the present invention has a DBP absorption of 10 to 50 (mL/100 g) and an iodine adsorption amount of 5 to 40 (mg/g). Ideally, the DBP absorption is 25 to 35 (mL/100 g), and the iodine adsorption amount is 10 to 30 (mg/g). The DBP absorption amount is described in JIS K6217-4:2001, and is expressed by the volume (mL/100 g) of DBP absorbed per 100 g. Further, the iodine adsorption amount is described in JIS K6217-1:2008, and is expressed by the amount of iodine (mg/g) adsorbed per unit weight of carbon black. They are all customary carbon black characteristics.

In general, carbon black exists in a state in which particles are welded to each other and is called an aggregate. Conceptually, a grape bunch is exemplified. The degree of development of this aggregate is called organization, and the indicator indicating the degree of development of the organization is the amount of DBP absorption. The iodine adsorption amount is the most representative index for determining the total specific surface area including the pores of the carbon black particles.

The smaller the amount of iodine adsorption, the smaller the specific surface area of the carbon black particles, and the lower the possibility that the particles in the resin composition contact each other. DBP absorption is small In the case, the degree of development of the organization is low, indicating that the connection between the particles is not developed. That is, even if carbon black having these characteristics is added to the resin in a large amount, the particles are easily insulated by the resin. Further, since the percolation threshold is high, the insulating property can be maintained, and it is considered that the resin composition can have dielectric properties such as a high dielectric constant and a low dielectric loss tangent.

In the case where the DBP absorption amount of carbon black is higher than 50 (mL/100 g) or the iodine adsorption amount is higher than 40 (mg/g), the carbon black particles in the resin composition are in contact with each other, and the frequency of electrical connection rises. The electrical loss tangent increases. This also means that the carbon black particles are easily dispersed poorly in the resin composition, so that the dispersion is poor during melt kneading, and the separated carbon black tends to adhere to the vicinity of the mold. As a result, it is difficult to stably produce the particles, and the appearance defects such as flow marks appearing in the injection molded article are difficult to obtain, and it is difficult to obtain a molded article excellent in appearance.

A well-developed carbon black is easy to obtain a resin composition having a high dielectric constant. However, there is a problem that the directionality of the aggregate causes an anisotropy of the dielectric constant, or a percolation causes a problem that the dielectric loss tangent increases. It is particularly unsuitable for use as an antenna member.

In the carbon black in which the DBP absorption amount is less than 10 (mL/100 g), when carbon black is produced, the adhesion of the carbon black particles to the manufacturing apparatus increases, and it is difficult to continuously operate (JP-A-2011-98995). Therefore, such carbon black is difficult to obtain stably. In addition, carbon black having an iodine adsorption amount of less than 5 (mg/g) is not sold at home and abroad, and it is difficult to purchase it stably.

The carbon black (b) used in the present invention is not limited as long as it has a specific DBP absorption amount and an iodine adsorption amount, and can be appropriately selected depending on the purpose. For example, an oil produced by incomplete combustion of a feedstock oil by an oil furnace method may be mentioned. Furnace black, acetylene black produced by a special furnace method, acetylene black produced by using acetylene gas as a raw material, lamp black produced by directly burning raw materials in a sealed space, and thermally decomposed by natural gas The hot carbon black is generated, and the diffusion flame is brought into contact with the groove black accumulated on the bottom surface of the channel steel. Commercially available products are "Asahi #8" or "Asahi thermal" (Xu Carbon Co., Ltd.) obtained by the furnace black method.

In one embodiment, the nitrogen adsorption specific surface area (N ₂ SA) of the (b) carbon black is preferably 5 to 40 m ² /g, more preferably 10 to 30 m ² /g. Similarly to the iodine adsorption amount, the nitrogen adsorption specific surface area is a total specific surface area of the carbon black, and is a useful carbon black characteristic index. The nitrogen adsorption specific surface area can be measured in accordance with JIS K6217-2. The nitrogen adsorption specific surface area of carbon black is in the above range, and is similar to the iodine adsorption amount in terms of dielectric constant, dielectric loss tangent, and the like.

Further, the ratio of the nitrogen adsorption specific surface area to the iodine adsorption amount (N ₂ SA/IA) is preferably less than 1.3, and preferably less than 1.1. By adding carbon black having a N ₂ SA/IA in the above range in an amount described later, a resin composition having a relatively excellent dielectric constant and dielectric loss tangent can be obtained. This resin composition can exhibit stable dielectric properties.

The resin composition (C) for a high dielectric constant material constituting the molded article of the present invention contains 40 to 80% by mass of the polycarbonate resin (a) and 20 to 60% by mass of the carbon black (b). The polycarbonate resin (a) is preferably 50 to 60% by mass and carbon black (b) is 40 to 50% by mass. As long as it is carbon black having the above specific DBP absorption amount and iodine adsorption amount, carbon black particles do not percolate in this range, and high dielectric constant and low dielectric loss can be obtained. Tangented resin composition. In addition, characteristics such as dielectric characteristics or percolation thresholds theoretically depend on the volume fraction. When the carbon black (b) content is 20 to 60% by mass, the volume fraction is approximately equivalent to 15 to 55% by volume.

A resin composition for a high dielectric material material constituting the molded article of the present invention (C) for improving the thermal stability of the resin composition during melt-kneading in the production and molding steps or in a high-temperature gas atmosphere when the product is used. Medium heat blending agent should be blended. The thermal stabilizer is preferably a hindered phenol compound, a phosphite compound, a phosphinate compound, or zinc oxide.

Further, other components may be further added as necessary in the resin composition (C) for a high dielectric material constituting the molded article of the present invention. Examples of such an additive include a filler, a reinforcing material, a weather resistance improver, a foaming agent, a lubricant, a fluidity improver, a wash resistance improver, a dye, a pigment, a dispersant, and the like. For example, fillers or reinforcing agents may be organic or inorganic, and glass fiber, mica (mica, biotite, phlogopite, etc.), alumina, talc, ettringite, calcium carbonate, and cerium oxide are usually used. Inorganic substances. These materials are preferably blended in an amount of from 1 to 100 parts by mass, preferably from 5 to 80 parts by mass, more preferably from 5 to 60 parts by mass, per 100 parts by mass of the total of the polycarbonate resin (a) and the specific carbon black (b). . When such a substance is blended, rigidity, heat resistance, dimensional precision, and the like are generally improved. In particular, muscovite or alumina among these is preferred because it has an effect of lowering the dielectric loss tangent. The blending amount of muscovite or alumina is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass.

In the polycarbonate resin (D) of the target material which is compounded with the resin composition (C) for a high dielectric constant material, it may be contained in order to improve the punching strength. There is an elastomer as a washability improving agent. The elastomer is not particularly limited, and a multilayer structure polymer is preferred. The multilayer structure polymer may, for example, be an article containing a (meth)acrylic acid alkylate polymer. These multilayer structure polymers are polymers produced by continuously performing multistage seed polymerization by, for example, sequentially coating a polymer in a subsequent stage of the polymer. The basic polymer structure is a polymer having an inner core layer having a crosslinking component having a low glass transition temperature and an outermost core layer composed of a polymer compound for improving the adhesion to the matrix of the composition. The component forming the innermost layer of the multilayer structure polymer is a rubber component having a glass transition temperature of 0 ° C or lower. Examples of the rubber component include a rubber component such as butadiene, a rubber component such as styrene/butadiene, a rubber component of an alkyl (meth)acrylate polymer, and a polyorganosiloxane polymer. A rubber component obtained by complexing an alkyl acrylate polymer or a rubber component obtained by using the same. Further, examples of the component forming the outermost core layer include an aromatic vinyl monomer or a non-aromatic monomer or a copolymer of two or more of these. Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methylstyrene, monochlorostyrene, dichlorostyrene, and bromostyrene. Among these, styrene is particularly suitable. Examples of the non-aromatic monomer include alkyl (meth)acrylate such as ethyl (meth)acrylate and butyl (meth)acrylate, vinyl cyanide or cyanide such as acrylonitrile or methacrylonitrile. Ethylene and the like.

Since the resin composition (C) for a high dielectric constant material contains a large amount of carbon black, the difference in shrinkage ratio with the target material may cause the two-color molded article to bend. In order to reduce the difference in shrinkage, it can also be used in the polycarbonate material of the target material. The inorganic filler is blended in the fat (D).

The resin composition (C) for a high dielectric material constituting the molded article of the present invention contains a polycarbonate resin (a) and a specific carbon black (b), and can be, for example, a polycarbonate resin (a) and a specific Carbon black (b) is produced by the steps of melt kneading. Further, it can also be obtained by a method of removing a solvent by a varnish formed by uniformly dispersing a solvent for dissolving the polycarbonate resin (a).

The carbon black (b) used in the present invention has a DBP absorption of 10 to 50 (mL/100 g) and an iodine adsorption amount of 5 to 40 (mg/g), but with ordinary carbon black exceeding the upper limit of the numerical range. The dispersibility in the molten resin is relatively good. Therefore, it is suitable for manufacture by melt-kneading by an extruder. Since carbon black does not function as a hydrolysis catalyst for a polycarbonate resin, the polycarbonate resin does not decompose even at a high temperature during melting, and the heat stability is good.

Melt kneading can be carried out by, for example, blending carbon black (b) in a polycarbonate resin (a), and if necessary, blending a heat stabilizer or an additive as described above, by a Henschel mixer, ribbon blending After uniformly mixing the machine, the V-type blender, etc., the uniaxial or multi-axis mixing extruder, the roll machine, the Banbury mixer, the Labo Plastomill mixer (Brabender mixer), etc. are heated, in a molten state. Perform a kneading process. In addition, several components may be mixed in advance, or may be supplied in a kneading process without pre-mixing, instead of mixing and kneading all the components together.

The kneading temperature and the kneading time vary depending on the resin composition (C) or the type of the kneading machine for the high dielectric constant material of the target, and are usually mixed. The training temperature is 200~350°C, preferably 220~320°C, and the mixing time is preferably less than 20 minutes. When the temperature exceeds 350 ° C or 20 minutes, thermal deterioration of the resin material may become a problem, and the physical properties of the molded article may be lowered or the appearance may be poor. In this way, particles of the resin composition (C) for a high dielectric material can be obtained.

The molded article of the present invention can be obtained by molding the resin composition (C) for the high dielectric constant material and the polycarbonate resin (D) in two colors. The two-color molding is a surface layer of a molded article of a primary material composed of one of a resin composition (C) or a polycarbonate resin (D) for a high dielectric constant material, and another material is used as a secondary material. Forming is carried out. For example, a resin composition (C) for a high dielectric material as a primary material is injection molded using a metal mold having a cavity length of 100 mm, a width of 100 mm, and a thickness of 1.5 mm. Further, a metal mold having a cavity length of 100 mm, a width of 100 mm, and a thickness of 3 mmt was used, and the molded body obtained by the above method was inserted into a metal mold, and then the polycarbonate resin (D) as a secondary material was injection molded. It is also possible to change the primary material to a polycarbonate resin (D) and the secondary material to a resin composition (C) for a high dielectric material. Further, the primary material may be an article formed by extrusion molding or an article which can be shaped by further thermoforming. The molding conditions of these molded articles are not particularly limited as long as they do not deteriorate the resin.

The two-color molded article contains a layered layer of a layer of a resin composition (C) for a high dielectric constant material and a polycarbonate resin (D). Since the layer of the polycarbonate resin (D) has a function of exhibiting impact resistance, it is preferable to have a layer thickness of 0.1 mm or more on the molded article. In addition, if it is too thick, it will There is a case where the Charpy is reduced. Therefore, the thickness of the layer should be 0.1 to 5 mm.

The molded article of the present invention is easy to manufacture. The appearance of the injection molded article is not good for flow marks or the like, and is suitable for the antenna component. The antenna circuit is formed on the resin composition (C) side for a high dielectric material of a two-color molded article. The resin material for the antenna only needs to have a desired dielectric property in a portion near the antenna circuit, and therefore has a dielectric constant even on the opposite side of the resin composition (C) layer for a high dielectric material. The high polycarbonate resin (C) layer has no effect on the performance of the antenna.

In order to reduce the size of the antenna component, the dielectric composition (C) for a high dielectric constant material has a dielectric constant of 4 or more, preferably 6 or more, more preferably 8 or more, and particularly preferably 9 or more. This is because if the dielectric constant is small, the antenna component cannot be made small enough. From the viewpoint of miniaturization, the upper limit of the dielectric constant is not particularly limited. However, if the dielectric constant is too large, the antenna size is too small. Therefore, it is preferably 30 or less in practical use, and preferably 14 or less, and 12 or less. For better, 11 or less is especially good. The smaller the dielectric loss tangent is, the higher the radio wave emission efficiency is emitted by the antenna, and the longer the battery is, the better the temperature is 0.05 or less, preferably 0.03 or less, and preferably 0.01 or less.

[Example B]

The second aspect will be further described in detail by way of examples, but the invention is not limited thereto. Further, in the following examples, the following components were used for the respective components.

Polycarbonate resin; products of Mitsubishi Engineering Plastics Co., Ltd. "Product Name: S-3000FN, viscosity average molecular weight 22,000"

Carbon black; manufactured by Asahi Carbon Co., Ltd., "product name: Asahi #8", DBP absorption amount 30 (mL/100g), iodine adsorption amount (AI) 12 (mg/g), nitrogen adsorption specific surface area (N ₂ SA ) 12 (m ² /g), N ₂ SA/AI 1.0

Thermal stabilizer; ginseng (2,4-di-t-butylphenyl) phosphite; Adeka Argus Co., Ltd., "trade name: ADK STAB 2112"

[Manufacture of Resin Composition (C) for High Dielectric Materials]

6 kg of polycarbonate resin (S-3000FN), 4 kg of carbon black (Xu #8), and 3 g of thermal stabilizer (ADK STAB 2112) were blended and uniformly mixed by a roller mixer. This was put into the upstream part of a twin-screw extruder ("KK30", manufactured by Nippon Steel Co., Ltd., screw diameter: 30 mm, L/D = 63), and was melt-kneaded at a cylinder temperature of 265 ° C and a screw rotation speed of 400 rpm to produce a mixture. A pellet of a resin composition (C) for a high dielectric constant material. There is no material bridge or the like at the raw material supply port, and it is stable, and the operating conditions and the resin pressure are not changed and are stable. The extruded resin strands can be granulated by a usual water-cooling tank, and it is not necessary to use a special mesh belt or the like. The following evaluation was carried out using the obtained pellets.

(1) Dielectric properties

The pellet of the resin composition (C) for a high dielectric material is put into an injection molding machine (made by Toshiba Machine Co., Ltd., IS100F, clamping force) 100 t) A plate-shaped molded article of 100 mm × 100 mm × 3 mm in thickness was produced under the conditions of a cylinder temperature of 290 ° C to 310 ° C and a mold temperature of 100 ° C. The dielectric constant and the dielectric loss tangent were measured at 1 GHz at room temperature using a substance analyzer (manufactured by Agilent, 4291A). The dielectric constant was 9.4 and the dielectric loss tangent was 0.0081.

(2) Appearance

The pellet of the resin composition (C) for a high dielectric constant material was placed in an injection molding machine (IS100F, manufactured by Toshiba Machine Co., Ltd., clamping force 100 t), and the cylinder temperature was 290 ° C to 310 ° C, and the mold temperature was 100. A plate-shaped molded article of 100 mm × 100 mm × 3 mm in thickness was produced under the conditions of °C. The appearance of the flow marks generated on the obtained molded article was visually evaluated. The evaluation is based on 5 points (5 points: very good, 4 points: good, 3 points: slightly good, 2 points: slightly bad, 1 point: bad), which is 5 points.

Examples B1 to B4 and Comparative Example B1

A primary material was polycarbonate resin (S3000-FN), and a square plate (100 × 100 mm) having a thickness of 1 mmt, 1.5 mmt, and 2 mmt was produced by injection molding. Using the same polycarbonate resin, a sheet having a thickness of 1 mmt was produced by extrusion molding and cut into a size of 100 × 100 mm. These four thickness primary materials were embedded in a metal mold having a cavity length of 100 mm, a width of 100 mm, and a thickness of 3 mmt. The secondary material is a resin composition (C) for the above high dielectric material, and is formed by injection molding to have a thickness of 3 mmt. Two-color molded article (Examples B1 to B4). In addition, a resin material (C) for a high dielectric constant material was injection-molded in the same metal mold, and a molded article having a thickness of 3 mm was obtained (Comparative Example B1). The following ball drop test evaluations were performed for each molded article.

(3) Falling ball test

The test was conducted based on JIS K7211. The surface of the resin composition (C) side for the high dielectric material of the two-color molded article was tested as the surface of the iron ball collision, and the calculation of the step method was used to calculate the 50% crushing energy E50, and the two-color molded article was evaluated. The characteristics of the rush. The results are disclosed in Table 3.

From the above, it is understood that the resin molded article for a high dielectric constant material of Examples B1 to B4 is excellent in not only the characteristics of the dielectric material but also easy to manufacture, and the molded article is excellent in appearance and excellent in punching resistance. On the other hand, Comparative Example B1 which was not formed by two-color molding was excellent in dielectric properties, but the punching property was extremely low, and it was not sufficient in terms of use of a mobile phone device or the like.

The molded article associated with the second aspect described above has excellent dielectric properties, and is particularly suitable as a high dielectric material for use in an antenna member requiring high dielectric constant and low dielectric loss tangent. In addition, since it can be molded into a molded product by two-color molding of polycarbonate having excellent punching characteristics, it is high in single height. Among the resin compositions for dielectric materials, the impact characteristics which are problematic are improved.

<3rd aspect>

The masterbatch for coloring associated with the third aspect of the present invention contains (E) carbon black and (F) resin material having specific physical properties. (E) Carbon black is characterized by a low DBP absorption.

(E) carbon black

The DBP absorption amount of the carbon black used in the present invention is 10 to 50 (mL/100 g), and ideally, the DBP absorption amount is 25 to 35 (mL/100 g). The DBP absorption amount is described in JIS K6217-4:2001. The measurement method is expressed by the volume (mL/100 g) of DBP (dibutyl phthalate) absorbed per 100 g, and is a conventional carbon black characteristic index.

In general, carbon black exists in a state in which particles are welded to each other and is called an aggregate, and a grape bunch is conceptually exemplified. The degree of development of this aggregate is called organization, and the indicator indicating the degree of development of the organization is the amount of DBP absorption. In the case where the DBP absorption amount of carbon black is higher than 50 (mL/100 g), it is difficult to disperse the carbon black particles at a high concentration. In addition, in the carbon black having a DBP absorption amount of less than 10 (mL/100 g), when carbon black is produced, the adhesion of the carbon black particles to the manufacturing apparatus increases, and it is difficult to continuously operate (JP-A-2011-98995).

(E) carbon black used in the present invention as long as it has specific DBP absorption The quantity is not limited and can be appropriately selected according to the purpose. For example, the oil furnace black produced by incomplete combustion of the feedstock oil by the oil furnace method, the acetylene black produced by the special furnace method, and the acetylene black produced by using acetylene gas as a raw material can be used in a sealed space. The lamp black produced by direct combustion of the raw material, the hot carbon black produced by thermal decomposition of natural gas, and the groove black accumulated by the diffusion flame contacting the bottom surface of the channel steel. Commercially available products are "Asahi #8" or "Asahi thermal" (Xu Carbon Co., Ltd.) obtained by the furnace black method.

Another indicator of the shape of carbon black is known to have an amount of iodine adsorption. The measurement method is expressed by the amount of iodine (mg/g) adsorbed per unit weight as described in JIS K6217-1:2008. The most representative index of iodine adsorption is expressed by the total specific surface area including the pores of carbon black particles, and has a certain degree of correlation with the amount of DBP absorption. The (E) carbon black used in the present invention preferably has an iodine adsorption amount of 10 to 30 (mg/g).

In general, carbon black which is widely used for imparting conductivity to a resin composition is suitable for a DBP absorption amount or an iodine adsorption amount. In contrast, the carbon black used in the present invention is characterized in that DBP absorption amount is limited. In the low range.

Further, the surface pH of the carbon black may be slightly alkaline or neutral to acidic, and in the case where the (F) resin material is polycarbonate or polyester, these resins tend to be hydrolyzed by a base. Therefore, (E) carbon black should be neutral to acidic, and the surface pH should be 3-8.

(F) resin material

The resin material of the present invention is desirably a thermoplastic resin. Can be listed, for example, low Density polyethylene, ultra low density polyethylene, ultra ultra low density polyethylene, high density polyethylene, low molecular weight polyethylene, ultra high molecular weight polyethylene, ethylene-propylene copolymer, polyolefin resin such as polypropylene, or poly Styrene resin, polyphenylene ether resin and polystyrene such as styrene, impact-resistant polystyrene, acrylonitrile/styrene copolymer (AS resin), acrylonitrile/butadiene/styrene copolymer (ABS resin) An alloy of a styrene resin, an alloy of a polyphenylene ether resin and a polyamide resin, a denatured polyphenylene ether resin such as an alloy of a polyphenylene ether resin and a polyolefin resin, or a polycarbonate resin. Other examples include a polyester resin represented by a polybutylene terephthalate resin or a polyethylene terephthalate resin, a polyamide represented by polyamine 6, a polyamine 66, and a polyamide MXD6. An engineering plastic such as a guanamine resin or a polyacetal resin or an alloy containing the same. Further, it is also possible to use a super-engineered plastic having high heat resistance such as a liquid crystal polymer, a polyphenylene sulfide resin or a polyimide resin, or an alloy containing the same.

As the resin material of the base resin for the master batch, as described later, only a resin such as polystyrene or AS resin is used. On the other hand, in the masterbatch for coloring of the present invention, the resin material can be used substantially without limitation by combining specific (E) carbon black. Among the above, a polycarbonate resin, a polystyrene resin, a polyamide resin, a polyester resin, or a polyacetal resin is suitable. From the viewpoint of adding a higher concentration of carbon black, polycarbonate resin is particularly preferred.

Carbon black has high agglutination, and aggregates are easily formed into two secondary aggregates (agglomerate) by Van Der Waals Force or by simple assembly, adhesion, complexation, and the like. In blending to In the case of the resin, the agglomerated structure is also maintained, and this is considered to be the cause of the "particles" in the molded article. The masterbatch containing a high concentration of (E) carbon black has a higher viscosity than the (F) resin material as a substrate, so that it is difficult to carry out strong kneading to destroy the agglomerated structure, and (F) resin material has been used for a long time. A low-viscosity material such as polystyrene, AS resin, or oligomer. However, in the case where the engineering plastic is colored by the master batch, since the viscosity of the (F) resin material is low or different from that of the colored resin, the mechanical properties of the resin composition may be lowered after mixing. Therefore, the (F) resin material is desirably of the same kind as the colored resin and has the same molecular weight.

Further, the melt viscosity of the (F) resin material used in the present invention is not particularly limited. Should be 100~2000Pa. s (280 ° C, 100 / sec).

In the masterbatch for coloring of the present invention, the content ratio of (E) carbon black to (F) resin material is not particularly limited, and usually (E) carbon black accounts for 10 to 90% by mass, and (F) resin material accounts for 10~90% by mass. The carbonaceous masterbatch for coloring needs to be able to contain a high concentration of carbon black, and the carbon black particles need to be dispersed in a state where they do not aggregate.

According to JIS K6217-4:2008, the smallest constituent unit of carbon black is a primary aggregate (aggregate) in which fine particles are welded. The more the number of particles per aggregate, the more developed the tissue. Aggregates have a complex structure of branches and therefore have a void portion whose volume is greater in the carbon black in which the tissue is more developed. The DBP oil is absorbed by the voids present in the aggregate, so the DBP absorption of the carbon black is the amount of DBP necessary to fill the voids of the aggregate. Therefore, the DBP absorption is an assessment of the degree of tissue development of carbon black. Methods. That is, in the case where the DBP oil mixed to the carbon black is less than the DBP absorption amount, the added DBP oil is absorbed in the voids, and thus becomes dry and hard to be collected. That is, the particles are agglomerated with each other, and the dispersed state is poor. Further, when the DBP oil to be added is equal to or higher than the DBP absorption amount, the DBP oil fills the voids, and the excess DBP oil exists between the aggregates, so that it can be in a good dispersed state. Even in the case of being dispersed in the resin, it is considered that the carbon black having a lower DBP absorption amount has a better dispersion state and can be added in a large amount. The higher the concentration of the master batch, the more the ratio of the (F) resin material contained in the master batch can be reduced, and it does not affect the properties of the colored resin, so it is suitable.

The (E) carbon black of a specific DBP absorption amount used for the coloring master batch of the present invention can be blended to the resin at a high concentration. Therefore, the content ratio of the (E) carbon black in the masterbatch for coloring of the present invention is preferably 40 to 90% by mass, and preferably 60 to 90% by mass. In this case, the content ratio of the (F) resin material in the coloring master batch is preferably 10 to 60% by mass, and preferably 10 to 40% by mass.

In order to enhance the thermal stability in the high-temperature environment during the production and molding steps of the resin composition or in the high-temperature environment, the thermal masterbatch of the coloring masterbatch of the present invention may be blended. The thermal stabilizer is preferably a hindered phenol compound, a phosphite compound, a phosphinate compound, or zinc oxide.

Further, a known ultraviolet absorber, other dyes, an antistatic agent, a flame retardant, a release agent, or an elastomer for improving the press, which are added to the resin composition, may be blended as necessary.

The masterbatch for coloring of the present invention contains a specific (E) carbon black and (F) resin material, and can be produced, for example, by a step of melt-kneading a specific (E) carbon black and (F) resin material.

The DBP absorption amount of the (E) carbon black used in the present application is 10 to 50 (mL/100 g), and the dispersibility in the molten resin is better than that of the ordinary carbon black exceeding the upper limit of the numerical range. Therefore, it is suitable for manufacture by melt-kneading by an extruder.

Melt kneading can be carried out by, for example, blending (E) carbon black, (F) resin material, further blending the heat stabilizer or additive as described above, by Henschel mixer, ribbon blender, After uniformly mixing the V-type blender, etc., heating is performed by a uniaxial or multiaxial mixing extruder, a roll mill, a Banbury mixer, a Labo Plastomill mixer (Brabender mixer), a pressurizing kneader, and the like. The mixing is carried out in a molten state. In addition, several components may be mixed in advance or may be supplied in a kneading process without mixing in advance, instead of mixing and kneading all the components together.

Regarding the mixing temperature and the mixing time, the mixing temperature is usually 200 to 350 ° C, preferably 220 to 320 ° C, and the mixing time is preferably 20 minutes or less. When the temperature exceeds 350 ° C or 20 minutes, thermal deterioration of the resin material may become a problem, and the physical properties of the molded article may be lowered or the appearance may be poor.

The obtained particulate master batch can be directly melted and kneaded with the colored resin to produce a colored molding material, or can be used by coarsely pulverizing it according to the properties of the colored resin by a pulverizer or the like. The bulk masterbatch obtained by the Banbury mixer or the pressure kneader can be made into a suitable particle diameter by coarse particle formation by a pulverizer or the like according to the properties of the resin to be colored. use.

The coloring resin to be colored is used as the coloring resin to be colored, and the same resin as the resin described in the above (F) resin material as the masterbatch base resin can be used. As described above, the colored resin is preferably the same as the resin material in the master batch.

According to an embodiment of the present invention, a molding material containing the above-mentioned coloring master batch and a colored resin can be provided. By using this molding material, a molded article corresponding to the use can be produced.

[Example C]

The above third aspect will be described in further detail by way of examples, but the invention is not limited thereto. Further, in the following examples and comparative examples, the following items were used for the respective components.

(E) carbon black

(e1) manufactured by Asahi Carbon Co., Ltd., "product name: Asahi #8", DBP absorption amount 30 (mL/100g), pH = 7.5, iodine adsorption amount 12 (mg/g)

(e2) manufactured by Mitsubishi Chemical Corporation, "product name: MA600", DBP absorption amount 115 (mL/100g), pH=7, iodine adsorption amount 40 (mg/g)

(F) resin material

(f1) polycarbonate resin

Mitsubishi Engineering Plastics Co., Ltd., "Product Name: H-4000FN"

Viscosity average molecular weight 16000, melt viscosity 250Pa. s (280 ° C, 100 / sec)

(f2) polycarbonate resin

Mitsubishi Engineering Plastics Co., Ltd., "Product Name: S-3000FN"

Viscosity average molecular weight 22000, melt viscosity 850Pa. s (280 ° C, 100 / sec)

(f3) Aromatic polyamide resin

Mitsubishi Engineering Plastics Co., Ltd. product, "trade name: RENY 6001", viscosity average molecular weight 17000, melt viscosity 100Pa. s (280 ° C, 100 / sec)

(G) heat stabilizer

(g1) phosphite antioxidant; manufactured by Adeka Argus Co., Ltd., "Product name: ADK STAB 2112"

(g2) hindered phenolic antioxidant; BASF Japan, Inc., "Product Name: IRGANOX 1098"

(H) colored resin

(h1) polycarbonate resin

Mitsubishi Engineering Plastics Co., Ltd. product, "trade name: S-3000FN", viscosity average molecular weight 22000

(h2) glass fiber reinforced aromatic polyamide resin

Mitsubishi Engineering Plastics Co., Ltd., "Product Name: RENY 1002H", (30% blended with glass fiber in RENY 6001)

Examples C1 to C7 and Comparative Examples C1 to C3

Carbon black, a polycarbonate resin, a polyamide resin, and a heat stabilizer were blended in a ratio shown in Table 4, and uniformly mixed by a roller mixer. This was put into the most upstream portion of a twin-screw extruder ("KK30", manufactured by Nippon Steel Co., Ltd., screw diameter: 30 mm, L/D = 63), and a masterbatch for coloring was produced by melt kneading. The extrusion kneading conditions are as follows.

(Examples C1 to C6): the cylinder temperature was 265 ° C, the screw rotation speed was 400 rpm, and the discharge amount was 20 kg/h.

(Example C7): The cylinder temperature was 270 ° C, the screw rotation speed was 300 rpm, and the discharge amount was 20 kg/h.

(Comparative Example C2): Since the discharge was unstable, it was changed to a cylinder temperature of 260 ° C, a screw rotation speed of 300 rpm, and a discharge amount of 2 kg/h.

(Comparative Examples C1 and C3): Since carbon was ejected from the vacuum vent hole, the production of the master batch was impossible.

The evaluation of the masterbatch for coloring is carried out by the ease of manufacture at the time of extrusion kneading.

(1) Masterbatch manufacturing difficulty

When (E) carbon black and (F) resin materials are mixed and melt-kneaded in a twin-screw extruder, the master batch is evaluated according to the following conditions according to the conditions of the extruder. Create difficulty. The results are disclosed in Table 4.

(Easy) The motor current is constant, the discharge amount does not change, and the strands are not broken. There were some volatiles in the vacuum vent, but the residue at the spout was hardly produced and the strands were not broken. There is almost no need for maintenance, but a state of stability.

(Difficulty) The situation that the spit is not stable, the strands are frequently broken, and it is difficult to manufacture continuously. In the case where a large amount of residual dirt is accumulated in the spout, it must be maintained frequently. It is manufactured intermittently, or the amount of discharge is reduced, and it can be manufactured in a small amount.

(Cannot be manufactured) (E) Carbon black and (F) resin materials cannot be melted and kneaded in the extruder, and carbon black is ejected from the vacuum vent holes. A small or unmanufacturable state.

Examples C1 to C7: (Easy) The extrusion characteristics were good, and the master batch was stably produced by discharging at 20 kg/h.

Comparative Example C2: (Difficult) When 20 Kg/h was discharged, the mixing of carbon black and the resin was unstable, and the resin strands were frequently broken. Therefore, the amount of the discharge was reduced to 2 kg/h to produce a master batch.

Comparative Examples C1, C3; (Unable to manufacture) Carbon was ejected from the vacuum vent of the extruder. Even if the extrusion conditions are adjusted, the strands cannot be continuously discharged.

Examples C8 to C14 and Comparative Example C4

The masterbatch M1 to M7 obtained in the examples C1 to C7 and the M8 obtained in the comparative example C2 were melt-kneaded with the colored resin in an extruder to form a molding material by blending the carbon black in an amount of 1.0% by mass. Using a twin-screw extruder ("TEX30 α" manufactured by Nippon Steel Co., Ltd., screw diameter 30 mm, L/D = 63), colored pellets were used at a cylinder temperature of 265 ° C, a screw rotation speed of 400 rpm, and a discharge amount of 20 kg/h. The form gives the shaped material. The obtained colored particles were injection molded, and (2) evaluation of the appearance of the molded article was performed. The results are disclosed in Table 5. Further, in Examples C8 to C13 and Comparative Example C4 in which the colored resin was polycarbonate S-3000FN, (3) evaluation of the punching resistance by Charpy impact strength was performed. The results are disclosed in Table 5.

(2) Appearance of molded article

The colored particles were dried at 100 ° C for 4 hours. Then, using a injection molding machine (made by Toshiba Machine Co., Ltd., IS100F, clamping force 100t), a plate shape of 100 mm × 100 mm × thickness 3 mm was produced under the conditions of a cylinder temperature of 290 ° C to 310 ° C and a mold temperature of 100 ° C. Product. For what is obtained The "particles" produced by the molded articles were visually evaluated for appearance.

The appearance evaluation is to obliquely illuminate the surface of the molded article, and to judge the degree of conspicuousness of the carbon black aggregated particles. The visual evaluation is performed with a score of 5 points (5 points; very good, 4 points: good, 3 points: slightly good, 2 points: slightly bad, 1 point: bad).

(3) Punching resistance (Charpy impact strength)

According to ISO179-1 and 179-2. The colored particles obtained by the above method were dried at 100 ° C for 4 hours. Then, a test piece of 10 mm × 80 mm × 4 mm in thickness was molded under the conditions of a cylinder temperature of 290 ° C to 310 ° C and a mold temperature of 100 ° C using an injection molding machine (IS100F, mold clamping force 100 t, manufactured by Toshiba Machine Co., Ltd.). The test piece was processed to form a notch, and the Charpy impact strength (kJ/m ² ) was measured at a temperature of 23 °C.

(formation appearance)

Examples C8 to C14: As a result of observing the surface state of the molded article, no particles were observed.

Comparative Example C4: Many particles (aggregated carbon black particles) were observed on the surface of the molded article.

(rushing strength)

Among the molded articles after Charpy's strength test, there was ductile damage (the sample after the test was not separated, and it was destroyed in a part of the connected state), and the brittle fracture (the sample after the test was completely broken and was Destruction). Among the examples C8 to C10 and C13, all of the five tested were ductile failure, and among the examples C11 to C12 and the comparative example C4, One of the five tested was fragile destruction.

The masterbatch for coloring which is related to the third aspect described above is easily mass-produced, and carbon black can be blended in a large amount. Further, among the molding materials obtained by mixing the masterbatch for coloring and the resin to be colored, the carbon black can be uniformly dispersed. Therefore, the molded article obtained from such a molding material is less likely to cause appearance defects such as "particles". Further, the molded article obtained by mixing the above-mentioned coloring master batch to the colored resin has a good punching strength.

Claims (18)

A resin composition for a high dielectric constant material, which is a resin composition for a high dielectric material containing (A) a resin material of 40 to 80% by mass and (B) a carbon black of 20 to 60% by mass, and the foregoing (B) The DBP absorption of carbon black is 10 to 50 (mL/100 g) and the iodine adsorption amount is 5 to 40 (mg/g), and the dielectric composition of the high dielectric constant material has a dielectric constant of 4 or more. The dielectric loss tangent is 0.05 or less. The resin composition for a high dielectric material according to the first aspect of the invention, which comprises the above (A) resin material in an amount of 50 to 60% by mass and the (B) carbon black in an amount of 40 to 50% by mass, the (B) carbon The black DBP absorption is 25 to 35 (mL/100 g) and the iodine adsorption amount is 10 to 30 (mg/g). The resin composition for a high dielectric material according to the first aspect of the invention, wherein the (B) carbon black has a nitrogen adsorption specific surface area of 5 to 40 m ² /g. The resin composition for a high dielectric material according to the first aspect of the invention, wherein the ratio of the nitrogen adsorption specific surface area of the (B) carbon black to the iodine adsorption amount is less than 1.3. A resin composition for a high dielectric material according to the first aspect of the invention, wherein the (A) resin material is a polycarbonate resin, a denatured polyphenylene ether resin, a polyphenylene sulfide resin or a polycarbonate/ABS alloy. . A resin composition for a high dielectric material according to claim 5, wherein the (A) resin material is a polycarbonate resin. A molded article containing items 1 to 6 as claimed in the patent application A resin composition for a high dielectric material according to any one of them. A molded article obtained by two-color molding of a resin composition (C) and a polycarbonate resin (D) for a high dielectric material according to claim 6 of the patent application. The molded article of the eighth aspect of the invention, wherein the molded article is composed of the resin composition (C) layer for the high dielectric constant material and the polycarbonate resin (D) layer, the polycarbonate The thickness of the resin (D) layer is from 0.1 mm to 5 mm. The molded article according to claim 8 or 9, wherein the resin composition (C) for the high dielectric constant material and/or the polycarbonate resin (D) contains an inorganic filler. A masterbatch for coloring, which comprises a masterbatch for coloring of (E) carbon black and (F) a resin material, and the DBP absorption amount of the (E) carbon black is 10 to 50 (mL/100 g), the aforementioned (E) The carbon black has an iodine adsorption amount of 10 to 30 (mg/g). For example, in the coloring masterbatch of claim 11, wherein the aforementioned DBP absorption amount is 25 to 35 (mL/100 g). The masterbatch for coloring according to the eleventh aspect of the invention, wherein the content of the (E) carbon black is from 10 to 90% by mass, and the content of the (F) resin material is from 10 to 90% by mass. The masterbatch for coloring according to Item 13 of the patent application, wherein the content of the (E) carbon black is 40 to 90% by mass, and the content of the (F) resin material is 10 to 60% by mass. For example, the masterbatch for coloring in the 11th article of the patent application, the former The resin material (F) is one or more selected from the group consisting of a polycarbonate resin, a polystyrene resin, a polyamine resin, a polyester resin, and a polyacetal resin. The masterbatch for coloring according to item 15 of the patent application, wherein the resin material is a polycarbonate resin. For example, the coloring masterbatch of claim 11 further contains a heat stabilizer. A molding material comprising the coloring masterbatch and the colored resin according to any one of claims 11 to 17.